Amidoalkylamine glyceride wax



United States Patent 3,255,219 AMIDOALKYLAMINE GLYCERIDE WAX Harland H.Young, Western Springs, and Kurt H. Spitzmueller, Clarendon Hills, Ill.,assignors to Swift & Company, Chicago, 11]., a corporation of IllinoisNo Drawing. Filed Jan. 8, 1962, Ser. No. 164,972 2 Claims. (Cl.260404.5)

This invention relates to fatty compositions and, more particularly, tofatty materials substituted with amino fatty amido radicals and to themanufacture of such compositions.

Condensation products of amines and fatty acids and derivatives thereofhave been prepared heretofore and have been found useful for a varietyof applications such as surface-active agents, corrosion inhibitors andin the production of resins.

It has now been found that a particular type of new condensation productderived from amines and fatty compositions having properties simulatingnatural waxes and synthetic waxes can be prepared from fatty amidoamines and fatty acids and derivatives thereof.

It is accordingly an object of this invention to provide new fattyacids, fatty acid esters, fatty acid amides and fatty alcoholssubstituted along the fatty chain with fatty amido amino radicals.

Another object of the invention is the provision of a method forproducing new fatty compositions having fatty amido amino radicalssubstituted along a fatty chain.

Additional objects of the invention if not specifically set forth hereinwill be readily apparent to those skilled in the art from the detaileddescription of the invention which follows.

Generally the compositions of this invention comprise chain substitutedhigher fatty acids, esters of such higher fatty acids, fatty amides andfatty alcohols having substituted on adjacent carbons in an aliphaticchain a hydroxyl group and a fatty amido amino group. This alpha amidoamino-hydroxy substitution may occur one or more times in a given fattychain, generally one to five times, and the fatty acid portion of thefatty amido amino radical, as well as the amido portion of the fattyamido amino radical, can be varied widely. The compositions are waxelikematerials exhibiting strong adherence to surfaces on which they aredeposited such as glass, metal, etc. The tackiness of many of thecompositions renders them very satisfactory for use as ingredients inwaxes, adhesives and in the lamination of porous and nonporous materialssuch as sheets of metal foil, insulation paper, etc.

More particularly, the compositions of the invention can becharacterized as higher fatty acids, esters of such higher fatty acids,higher fatty alcohols and, higher fatty amides having chain substitutedhydroxyl and amido amino groups characterized by the structure:

I NH OH where Y is selected from the group consisting of aliphatichydrocarbon chains containing 1-6 carbons either unsubstituted or havingaliphatic hydrocarbon side chains, and amino alkylene radicals of 1-18carbon atoms and l-8 nitrogen atoms and R is an aliphatic hydrocarbonradical of 927 carbons.

The composition prepared by condensing the monoamide of 1,3 diaminopropane and stearic acid with "ice epoxidized butyl oleate, for example,can be represented by the structure (Ill-I2 CllHz NH OH Amino amidescontemplated as the amine supplying reactants in the formation of thewaxy condensation products are generally fatty acid monoamides ofaliphatic polyamines. Suitable fatty acids include those of the typel028 carbon saturated and unsaturated .monocarboxy-lic aliphatichydrocarbon acids such as .lauric, myristic, palmitic, margaric,stearic, arachidic, undecylenic, oleic, la'uroleic, palmitoleic,ricinoleic, myristoleic, linolenic, linoleic, gadoleic and erucic acid.The saturated, monoethenoic, diethenoic and triethenoic acids all can beemployed. The fatty acids and mixtures of fatty acids derived fromnaturally occurring animal, vegetable and marine triglycerides such ascoconut oil, palm oil, castor oil, cotton seed oil, soybean oil, linseedoil, safflower oil, tall oil, tallow, herring oil, sardine oil and whaleoil represent a convenient source of the higher fatty acids. Thepartially and completely hydrogenated derivatives of these triglyceridesare also contemplated.

Polyamines useful in forming the amido amines include those straightchain aliphatic olyamines having more than one amino nitrogen and havingfrom 2l0 carbon atoms. Typical non-hydroxylated aliphatic polyamineswhich can be employed in the formation of the amine substituted amidesinclude ethylene diamine, propylene diamine, butylene diamine, 1,3diamino propane, 1,3 diamino hexane, tetramethylene diamine, ditheylenetriamine, dipropylene triamine, triethylene tetramine, pentamethylenediamine, tetraethylene tetramine, tetraethylene pentamine pentaethylenehexamine, nonaethylene decamine, and other primary and secondaryaliphatic diamines, triamines, tetramines, pentamines and hexamines.Also suitable are the N-alkyl amino alkylamines. There is no particularlimit on the number of carbons and amino groups in the polyalkylenepolyamines which can be used but because of the lack of availabilitycompositions having about 2-18 carbons and 2l0 nitrogens arerecommended.

The amine reactive fatty derivatives employed in formation of thewaxlike compositions comprise higher fatty acid derivatives having aminereactive substituents such as oxirane groups or halohydroxy groups onthe fatty chain. Oxirane substituted higher fatty acids and higher fattyacid derivatives include those compositions such as partially andcompletely epoxidized higher fatty acids, esters, alcohols, etc., whichcontain one or several epoxy groups at those places in the moleculewhich before epoxidation existed as ethylenic unsaturation.

Esters of higher epoxy fatty acids such as those produced by theepoxidation of animal, vegetable and marine glycerides comprise atypical group of derivatives capable of reacting with the amino alkylacid amides. The lower aliphatic alcohol esters of such acids can alsobe employed as the amine reactive composition. Lower monohydric alcoholesters having 18 canbons in the alcohol, as well as dihydric alcoholesters having l-8 carbons, can also be employed. The trihydric,tetrahydric, pentahydric and hexahydric alcohol esters are alsosatisfactory materials for reactions with the amine substitutedmonoamide.

The epoxidized naturally occurring glyceride esters of higher fattyacids represent a very satisfactory source for this component of thecompositions because of their ready availability.

The halohydroxy fatty acids and derivatives thereof are less preferredamine reactive materials but again represent a large group from whichselection can be made. Included within this group are the higher fattyacids and derivatives of such higher fatty acids having hydroxy and halogroups substituted on at least one fatty chain. The chlorinesubstituents are preferred over the bromine and iodine substituentsinsofar as the halo group is concerned. The materials are prepared byadding a hypohal-ous acid across the double bonds of an unsaturatedfatty acid or derivative thereof such as undecylenic acid, palmitoleicacid, ricinoleic acid, oleic acid, petroselinic acid, linoleic acid,linolenic acid and arachidonic acid. The fatty acid components for boththe halohydroxy and the epoxy fatty acid derivatives are substantiallythe same. Both the epoxidized fatty acid and halohydroxylated fatty acidare prepared by known reactions. Very desirable epoxidized orhalohydroxylated derivatives are obtained by epoxidizing orhalohydroxylating naturally occurring glycerides having ethylenicunsaturation. Suitable animal, vegetable and marine triglycerides which,when treated with epoxidizing reagents or halohydroxyl-ating reagents toproduce the corresponding epoxides or halohydroxylated compounds aresoybean oil, cotton seed oil, tallow, linseed oil, safflower oil,herring oil, sardine oil, tung oil, and tall oil among others.

The compositions of the invention can be prepared by reacting themonoarnide of an aliphatic polyamine and a long chain fatty acid orfatty acid ester with a fatty composition having amine reactivesubstituents on a fatty chain. The amino amides are prepared by heatingand reacting a polyarnine with a higher fatty acid or higher fatty acidester until the carboxyl group is amidated and a fatty acid amide havingan available amine substituent is formed. The reaction is promoted byheating approxi mately molar equivalents of the fatty acid and amine or:by heating about molar equivalents of the amine with an ester of suchhigher fatty acids. stoichiometric amounts are generally preferredalthough a slight excess of the polyamine supplying material ispreferred to depress the amount of diamide formed as an undesired byproduct. In some cases %1 mole of the acid will be reacted with /2-3moles of the polyamine. Heating of the reactants either in the presenceof a solvent or in the absence of a solvent to a temperature sufficientto initiate reaction is suflicient to produce the amino amides.Ordinarily a temperature above about 100 C. will be employed and thereaction mixture will be agitated. Completion of the reaction is morerapidly attained at higher temperatures while lower reactiontemperatures require longer reaction times. Any amine volatilized duringthe course of the reaction should in the interest of economy be returnedto the reaction zone. It has been :found that the reaction can becarried out very easily and the reaction time shortened by the use ofsuperatmospheric pressures. Under such conditions of about -300 poundsper square inch pressure and temperatures in the range of 150-2l5 C., asmooth reaction with good yields and without loss of the more volatileamine is realized.

The amino monoamide and epoxidized fatty material are reacted by heatingthe monoamide having amino groups and about a stoichiometric amount ofthe epoxide at a temperature above about 100 C. for 1-5 hours or untilthe epoxy content of the oxirane containing material reaches a minimum.By stoichiometric amount of the epoxide, it is intended that enough ofthe epoxy derivative be employed to insure that one epoxy group bepresent for each available amino group in the amino amide. Thecondensation reaction proceeds much more slowly at 100 C. than at highertemperatures and is usually completed in about one hour at 200 C.superatmospheric conditions (20200 pounds per square inch) are preferredinasmuch as undesirable. side reactions can be minimized if the reactionis conducted under positive pressure.

The reaction between the oxirane containing material and the monoamideis particularly useful in the treatment of hard waxes such as thosecharacterized as fatty acid diamides of 1,3 diamino propane. These hardWaxes are disclosed and claimed in a copending application. In thepreparation of the hard waxes a small amount of residual monoamide ispresent in the wax and the epoxy material when reacted with themonoamide enhances the adhesion of the hard wax to smooth surfaces.

The following examples which are included herein for purposes ofillustrating the invention show the production of some of the waxyproducts of the invention.

Example I One mole (284 grams) of stearic acid are mixed with one mole(74 grams) of 1,3 diamino propane and heated with stirring in a pressurevessel. The reaction is run for 2 hours at 200 C. The pressure does notexceed 170 p.s.i. which represents the steam pressure from the water ofreaction. At the conclusion of the reaction period, the product iscooled to about C. and transferred to a steam deodorizer. Thedeodorization is carried out at 2-5 mm. mercury pressure using steam asthe stripping agent. The temperature is gradually raised to 200 C. toyield essentially N-stearoyl-1,3 diamino propane. This product istransferred to a pressure vessel and reacted with 176 grams ofepoxidized linseed oil having an oxirane content of 9.1%. After heatingat 200 C. for 5 hours with stirring the product is cooled to 150 C.before being exposed to the air. The final product is a firm but tackywax like material.

Example II One third of a mole (313 grams) of hydrogenated fish oil arereacted in a pressure vessel at 215 C. with one mole (74 grams) of 1,3diamino propane. The contents of the vessel is heated and stirred for 3hours during which time the maximum presure does not exceed 30 p.s.i. Atthe conclusion of the reaction period, the product is cooled to below150 C. and transferred to a deodorizer where the librated glycerol isremoved by the use of steam and vacuum. When the temperature reaches 200C. and the pressure drops to 1-2 mm. Hg, the stripping can be consideredessentially complete. The product is cooled under vacuum to l30-150 C.and poured into pans to yield substantially pure hydrogenated fish oilfatty acid monoamide of 1,3 diamino propane. The product is assayed bytitrating a sample in boiling neutral isopropyl alcohol and titratingwith N/2 hydrochloric acid using bromo cresol green as an indicator. Toa quantity of this monoamide containing one mole equivalent ofamino-groups are added 229 grams of epoxidized soya bean oil having anoxirane content of 7%. This supplies an equivalent amount of oxiranecontent to react with each amino group. The mixture is then heated in asealed vessel with stirring at 150 C. for 5 hours. At the conclusion ofthe reaction period, the product is cooled in trays to yield an adheringwax which will fracture when subjected to a sharp blow.

Example Ill One mole of 58 titre hydrogenated tallow (876 grams) isplaced in a pressure vessel with one and one-half moles of 1,3 diaminopropane (114 grams). The reaction is run with agitation for 2 hours at200 C. The pressure does not exceed 20 p.s.i. since water is not aby-product. At the end of the reaction time, the product is blown intothe deodorizer where free glycerine settles out. The product is thendeodorized with steam at a pressure of 5 mm. Hg and a temperature of 200C. The vapors of the deodorization are conducted through an aircondenser and finally through freezing trays to a vacuum source. Viscousglycerine distills and condenses in the air condenser starting at about150 C. This removal of glycerine accelerates with rising temperature,reaching a maximum at 175-180 C. in about 1 hour. The temperature isslowly increased to 200 C. by which time no further glycerine comesover. The heat source is removed and the contents of the deodorizer arecooled under vacuum in a continuing atmosphere of water vapor. At 140 C.the product is removed and chilled in a cold metal tray.

Glycerine recovered from the air condenser is 87% of the theoreticalquantity and titration of the total condensate indicates the loss ofamine as being less than 2%. A product made in this manner assays about10% as monoamide. Such a wax separates from any hard smooth surface butcan be given adhering properties by reacting the mono amide amineportion with epoxidized fats. Thus, the above product, about 900 grams,contained 90 grams of the amino-amide (0.28 mole) which in turn willrequire 4.47 grams of oxirane oxygen or 64 grams of epoxidized soya beanoil. The reactants in this ratio were heated in a pressure vessel at 150C. for 3 hours. After cooling to 140 C., the product is cast onto traysfor cooling. The product has adhering properties but can be removed byvigorous scraping. Analysis for oxirane content shows that practicallyall of the oxirane oxygen groups have reacted.

Example IV One mole of coconut oil (654 grams) and three moles of 1,3diamino propane (222 grams) are placed in a pressure vessel and heatedfor 5 hours with stirring at 150 C. The product is then stripped ofglycerine under vacuum using steam and the product used directly forreacting with 600 grams butyl epoxystearate (8% oxirane). The mixture isheated in a pressure vessel for 3 hours at 150 C. The final product is ahighly plasticized, adhering waxlike composition.

Example V One mole of castor oil fatty acids (296 grams) are reactedwith 1 mole of 1,3 diamino propane (74 grams) at 215 C. for 3 hours withagitation under pressure. Upon completion of the reaction, the pressurewhich has built up to 190 p.s.i., is released and the product cooled to150 C. in the absence of air. The cooling creates a slight vacuum whichis utilized to draw 178 grams of epoxidized linseed oil (16 g. oxiraneoxygen) into the pressure vessel. The reactants are reheated to 210 C.for 2 hours with agitation. At the completion of the reaction, theproduct is deodorized with steam at 200 C. and 5 mm. Hg pressure toremove impurities. Upon cooling, waxlike product is cast into slabs.

Example VI One mole of castor oil (934 grams) and three moles ofethylenediamine (180 grams) are reacted at 180 C. under pressure. Thereaction product is used directly for reaction with epoxidized linseedoil. Thus 533 grams of epoxidized linseed oil are added and heated withstirring until the epoxide content reaches a minimum, usually 2 hours at200 C. The final product is steam deodorized at ISO-200 C. and 2-5 mm.Hg pressure to remove odors and volatile by-products.

Example VII One mole (280 grams) of linoleic acid are reacted with onemole (114 grams) of 1,3 diaminopropane at 200 C. for 3 hours. Thereaction is carried out in a pressure vessel with agitation. Thepressure of the water vapor produced does not exceed 200 p.s.i. At theend of the three hour reaction period, the water vapor is vented untilthe internal pressure is equalized. 297 grams of epoxidized oleylalcohol (containing 5.4% oxirane oxygen) are pumped into the reactor andreacted with the amino amide by heating to 100 C. for five hours withagitation. At the completion of the reaction, the product is run intosuitable molds to yield a tough, tacky somewhat pliable wax.

6 Example VIII One mole of erucic acid (332 grams) and one mole ofbutylene diamine grams) are heated at C. for 5 hours. The pressure isvented periodically to allow most of the water to escape. A small amountof amine is lost simultaneously but this is of no practicalsignificance. At the end of the reaction period the pressures areequalized and one mole of methylchlorohydroxystearate (348 grams) isintroduced. The reaction is completed by heating for 3 hours at 150 C.followed by 2 hours at 200 C. After venting, the product is deodorizedat 150-200 C. and 2-5 mm. Hg pressure. After cooling to C., the productis cast into slabs to yield a high melting but tacky wax.

Example IX One mole of palmitic acid (256 grams) and one half mole (37grams) 1,3 diamino propane are heated in a pressure vessel withagitation at 215 C. for 4 hours. The product is cooled to 150 C. anddeodorized at 25 mm. Hg pressure at 150200 C. The final product hasabout 3% monoamide amino compound as determined by titration. Thereaction product is returned to the pressure vessel and reacted with 5.4grams of epoxidized linseed oil (0.03 moles oxirane oxygen) at 200 C.for 2 hours. The final product after cooling to 150 C. is drawn offyielding an essentially net-ural high melting wax with enhanced adhesiveproperties.

Example X One mole (938 grams) of castor oil and 3 moles (507 grams) oftetra ethylenepentamine are heated under pressure with agitation at 160C. for 5 hours. The reaction product is stripped of its free glycerol bya steam deodorization under vacuum. To the waxy product are added 3moles (685 grams) of epoxidized soya bean oil (oxirane oxygen=7%) andthe mixture heated at 180 C. for 3 hours to react with all primary aminofunctions. The wax made by such a process has excellent tack but lendsitself to easy removal by solutions having a low pH.

Example XI One mole of undecylenic acid (184 grams) and one mole of 1,5diamino pentane (82 grams) are heated in a pressure vessel with stirringto C. for 4 hours. The volatile by-products are steam stripped in adeodorizer under vacuum at 200 C. for 15 minutes. The final product iscondensed with one mole of 9,10 (10,9) chlorohydroxy stearyl alcohol(321.5 grams) by heating 150 C. for 5 hours. The reaction product is amedium melting point wax having good adhering properties with a certainamount of fungicidal properties.

As has been mentioned previously, the compositions of the inventionpossess a high degree of polarity and therefore adhere Well to smoothsurfaces such as glass and metal. The Wax-like materials which aresimilar in many respects to beeswax are mildly basic in reaction andafford good protection against corrosion to surfaces on which they arecoated.

Obviously many modifications and variations of the invention ashereinbefore set forth may be made without departing from the spirit andscope thereof and therefore only those limitations should be imposed asare indicated in the appended claims.

We claim:

1. A waxlike glyceride prepared by the process of reacting a monoamideof a C -C fatty acid and an alkylene polyamine consisting of carbon,hydrogen and nitrogen and having 2-28 carbons and 2-10 nitrogens aminogroup attached to adjacent carbons in said chain, said chain havingabout 1-5 of said groups, said amido amino groups having the structure 0H R( il 1'YNH- wherein Y is selected from the groups consisting ofalkylene radicals of 1-6 carbons and amino alkylene radicals of 1-8carbons and 1-8 nitrogen atoms and R is an aliphatic radical of 9-27carbons, said glycerides being prepared by reacting a monoamide of a C-C fatty acid and an alkylene polyarnine consisting of carbon, hydrogenand nitrogen and having 2-18 carbons and 2-10 nitrogens with a fattycomposition selected from the group consisting of epoxidizedtriglycerides having 9-27 carbon atoms in each alkyl chain andhalohydroxylated triglycerides having 9-27 carbon atoms in each alkylchain, said reaction being conducted at a temperature of between about100 C. and 200 C. for about 1-5 hours whereby to produce said waxlikeglycerides.

References Cited by the Examiner UNITED STATES PATENTS CHARLES B.PARKER, Primary Examiner.

ABRAHAM H. WINKELSTEIN, Examiner.

RAYMOND N. JONES, ROBERT V. HINES,

Assistant Examiners.

1. A WAXLIKE GLYCERIDE PREPARED BY THE PROCESS OF REACTING A MONOAMIDEOF A C10-C28 FATTY ACID AND AN ALKYLENE POLYAMINE CONSISTING OF CARBON,HYDROGEN AND NITROGEN AND HAVING 2-28 CARBONS AND 2-10 NITROGENS WITH AFATTY COMPOSITION SELECTED FROM THE GROUPS CONSISTING OF EPOXIDIZEDGLYCERIDES AND HALOHYDROXYLATED GLYCERIDES, SAID RECTION BEING CONDUCTEDAT A TEMPERATURE OF BETWEEN ABOUT 100*C. AND 200*C. FOR ABOUT 1-5 HOURSWHEREBY TO PRODUCE SAID WAXLIKE GLYCERIDE.